用分光光度法测量碳酰肼及孔雀石绿与碳酰肼的缩合反应动力学

用分光光度法研究了(15.0～22.0) ℃温度区间，水溶液中孔雀石绿和碳酰肼的缩合反应动力学。结果表明：此反应为二级反应，对于反应物分别为一级反应，离子强度在(0.2～1.0) mol·L^-1内对该反应产生负盐效应。提出了孔雀石绿和碳酰肼的反应机理。据此机理导出的速率方程与实验结果相吻合。在此基础上提出了测量碳酰肼浓度范围在(0.02～0.5)×10^-3 mol·L^-1的分光光度法。     

孔雀石绿在CPB胶束介质中的电化学行为

以玻碳电极(GCE)为工作电极,用循环伏安法(CV)研究了孔雀石绿(MG)在溴代十六烷基吡啶(CPB)胶束介质中的电化学行为,并与其在磷酸盐缓冲溶液(PBS)中的电化学行为进行了比较。在20～300mV/s范围内MG的氧化峰电流Ip与扫描速度平方根成正比,表明MG在GCE上的电化学氧化反应是一个受扩散控制的电化学过程。通过介质pH值对MG电化学氧化反应的影响研究发现,在pH值为4～8范围内MG的电化学氧化过程没有质子参与。用计时库仑法(CC)、计时电流法(CA)测定了有无CPB存在时MG的扩散系数D分别为2.34×10-6和2.51×10-6cm2/s,电荷转移系数α分别为0.56和0.72,电极反应速率常数kf为3.95×10-4和9.12×10-4s-1。结果表明,在PBS浓度较大的体系中,CPB更早的到达CMC且MG平台部分的氧化峰电流Ip较低;MG在2.0×10-2～8mmol/L浓度范围内,其氧化峰峰电流Ip随浓度增大降低,峰电位Ep正移。     

新型仿生光催化剂HMS-FePcS催化降解孔雀绿的反应因素及动力学

在可见光照射下,应用合成的新型仿生光催化剂HMS-FePcS,催化降解孔雀绿模拟废水.考察了温度、光源强度、催化剂用量、过氧化氢用量以及金属活性中心(Fe,Cu和Co)等一系列因素对降解反应的影响,得到了优化的反应条件.在此基础上推导出孔雀绿光催化降解的反应级数及反应速率常数.该降解反应分两个阶段,初始反应的速率与反应物的浓度无关,呈现出零级反应的特征;而后一阶段的反应呈现一级反应的特征.两段反应均可用经典的Langmuir-Hinshelwood多相催化动力学模型进行合理的解释.     

Study of Interactions and Association Thermodynamics Between Sudan Red and Sodium Dodecyl Sulfate in Microemulsions

The absorption spectrum of Sudan red III (SR) in oil solutions and a series of O/W microemulsion with surfactant sodium dodecyl sulfate (SDS) has been determined by the UV-Vis spectrophotometer. We found that an association interaction existed between the stain SR and anionic surfactant SDS in water/mixed oil/SDS microemulsions. By measuring the absorbance of Sudan red in a series of microemulsions which has different R values and using the appropriate association models to analyze the experimental data, we obtain the association constants of SR and SDS, and the values of thermodynamics functions of associationΔ_r G _m has also been calculated from the association constants.     

Thermodynamics and Kinetics of Bacterial Cellulose Adsorbing Persistent Pollutant from Aqueous Solutions

The adsorption capability of bacterial cellulose(BC) for anionic dye acid fuchsine was studied. Meanwhile, the processes of the adsorption were investignted and fitted by adsorption isotherm models, adsorption thermodynamics and adsorption kinetics models, respectively. The changes of BC before and after adsorbing acid fuchsine were investigated via scanning electron microscopy(SEM) and Fourier transform infrared spectroscopy(FTIR) to further explain the adsorption mechanism. The results show that acid fuchsine could be effectively adsorbed by BC. The adsorption process was fitted well by Langmuir equation and the pseudo-second order kinetics, indicating that the adsorption process was monolayer molecule adsorption with the main action of chemical adsorption. The adsorption process was spontaneous and endothermic. Glucuronic acid groups and hydroxyl groups were responsible for the adsorption of acid fuchsine on BC.     

Study on Preconcentration of Trace Copper Using Microcrystalline Triphenylmethane Loaded with Malachite Green

The paper describes a novel method for copper preconcentration using microcrystalline triphenylmethane loaded with malachite green prior to the determination by the flame atomic absorption spectrometry （FAAS）. Under the optimum conditions, Cu（Ⅱ） can be totally adsorbed on the surface of microcrystalline triphenylmethane, and completely separated from Pb（Ⅱ）, Cd（Ⅱ）, Co（Ⅱ）, Cr（Ⅲ）, Ni（Ⅱ）, Mn（Ⅱ）, Fe（Ⅲ） and Al（Ⅲ） by controlling acidity. The preconcentration factor of this proposed method is 200. The recovery is in a range of 97.5%-105%. The relative standard deviation （RSD） is not beyond 3.0%. The proposed method has been successfully applied to the determination of trace copper in various water samples with satisfactory results.     

Kinetics of Cathodic Reduction of Hypophosphite Anions in Aqueous Solutions

The kinetics of the cathodic reduction of hypophosphite anions in aqueous solutions is studied as a function of the electrode nature, the sodium hypophosphite concentration, and the solution pH. It is shown that the product of the reduction of hypophosphite anions is phosphorus. A scheme is proposed for the reduction process, according to which the phosphorus formation can proceed via two parallel routes—electrochemical and chemical—whose realization depends on the nature of the metal catalyst.     

MX—NX2和MX—NX3电解质水溶液的热力学研究

本文用Pitzer方程研究相同阴离子的非对称性混合电解质溶液的热力学性质,讨论了高次静电项(~Eθ_(ij)、~Eθ′_(ij))所产生的效应。引入混合参数(θ_(ij))和离子强度(Ⅰ)的关系式,估算了25℃时MX-NX_2和MX-NX_3电解质水溶液的Pitzer混合参数~Sθ_(ij)~(0)、~Sθ_(ij0~(1)和φ_(ij)k,其计算值和文献值吻合。     

绿色表面活性剂——烷基(聚)葡糖苷缔合结构体系

行近年来“绿色表面活性剂”烷基（聚）葡萄苷的研究在国际上越来越受重视。本文从表面吸附性能、水溶液的相行为、形成微乳液及与类脂物的作用等方面对烷基（聚）葡萄苷的研究进展作了综述。     

高效液相色谱双波长法同时测定水产品中孔雀石绿和隐性孔雀石绿

通过紫外可见分光光度计扫描,发现孔雀石绿和隐性孔雀石绿的最大吸收波长分别为620 nm和260 nm。在相应的最大吸收波长处,采用高效液相色谱-双波长紫外可见检测器对水产品中孔雀石绿和隐性孔雀石绿同时测定。结果表明,水产品中孔雀石绿和隐性孔雀石绿回收率分别为83%~89%和87%~93%,相对标准偏差分别为2.12%~2.53%和2.16%~2.65%,检出限分别为1μg/kg和2μg/kg。     

苯在Pluronic F127和P123胶束水溶液中的增溶动力学

发展了不分离胶束的增溶动力学数据分析模型,以此考察苯在F127和P123胶束水溶液中的增溶动力学行为.实验发现,这二种胶束增溶苯的速度较快,温度升高进一步促进了增溶.     

Dummy Template-Based Molecularly Imprinted Membrane Coating for Rapid Analysis of Malachite Green and Its Metabolic Intermediates in Shrimp and Fish

A novel malachite green molecularly imprinted membrane (MG-MIM) with specific selectivity for malachite green (MG) and leucomalachite green (LMG) was prepared using a hydrophobic glass fiber membrane as the polymer substrate, methyl violet as a template analog, 4-vinyl benzoic acid as the functional monomer, and ethyleneglycol dimethacrylate as the crosslinking agent. MG-MIM and non-imprinted membrane (NIM) were structurally characterized using scanning electron microscopy, surface area analyzer, Fourier-transform infrared spectrometer and synchronous thermal analyzer. The results showed that MG-MIM possessed a fluffier surface, porous and looser structure, and had good thermal stability. Adsorption properties of MG-MIM were investigated under optimal conditions, and adsorption equilibrium was reached in 20 min. The saturated adsorption capacities for MG and LMG were 24.25 ng·cm⁻² and 13.40 ng·cm⁻², and the maximum imprinting factors were 2.41 and 3.20, respectively. Issues such as “template leakage” and “embedding” were resolved. The specific recognition ability for the targets was good and the adsorption capacity was stable even after five cycles. The proposed method was successfully applied for the detection of MG and LMG in real samples, and it showed good linear correlation in the range of 0 to 10.0 μg·L⁻¹ (R² = 0.9991 and 0.9982), and high detection sensitivity (detection limits of MG and LMG of 0.005 μg/kg and 0.02 μg·kg⁻¹ in shrimp, and 0.005 μg/kg and 0.02 μg/kg in fish sample). The recoveries and relative standard deviations were in the range of 76.31–93.26% and 0.73–3.72%, respectively. The proposed method provides a simple, efficient and promising alternative for monitoring MG and LMG in aquatic products.     

Interactions between bromophenol blue and cetyl- trimethylammonium bromide in aqueous solutions and microemulsions

The UV-Vis light absorption spectroscopy of bromophenol blue (BPB) in a series of cetyltrimethylammonium bromide (CTAB) aqueous solutions and microemulsions has been determined. There exist association interactions between the BPB and cationic surfactant CTAB. By establishing the appropriate association models and measuring the absorbance in different concentrations of BPB aqueous solutions and microemulsions that have different R values, the association constants K were obtained and the values of thermodynamics functions of association Δ_rG_m were calculated. It shows that the formation of microemulsion has inhibitory effects on the association reaction.     

酶促反应动力学教学刍议:米氏方程衍生公式与图像

许多国内外高校的本科教学缺乏对米氏方程的深入推衍,这对学生了解酶促反应的动态过程及在实际科研工作中的应用是极为不利的。从酶促反应方程出发对米氏方程进行推导,继之采用双倒数法、单倒数法、直接隐函数法、间接隐函数法以及积分法对米氏方程进行线性化,得到适用于不同情况的衍生方程。从数学和酶学角度出发指出了不同方程的优势和缺点,并针对其缺陷提出了若干解决方案以及在实际应用过程中的注意事项。希对高校中有志于科研事业的相关专业的教师学生有所助益。     

沸石与酸性水溶液反应的动力学机制

利用连续搅拌筒反应器(CSTR)对天然沸石与酸性水溶液的反应动力学进行研究, 通过改变流速、 pH值等参数, 对反应速率进行计算和比较. 同时利用二次离子质谱(SIMS)、扫描电镜(SEM)对反应后的沸石表面进行分析研究. 实验结果表明, 沸石中的Si、Al、Na的释放速率在多数情况下不相同, 沸石的溶解为不一致溶解作用. 25 ℃、1.01×10⁵ Pa条件下, 硅的释放速率为：在pH=2.45溶液中反应时, -rSi=kS(aH+)1.25/ (aSi)0.60；在pH=3.26溶液中反应时, -rSi=kS(aH+)1.50/(aSi)0.25(S为矿物材料的表面积). SIMS研究显示, 天然沸石与酸性水溶液的反应中, 在沸石表面Si、Al、Na在100 nm的厚度范围内, 随着离表面距离的改变, 在近表面范围内Na、Al大量淋失, 有H⁺浸入. 此外, SEM分析结果显示, 天然沸石与纯水及酸性水溶液反应后, 表面形貌显著不同.     

Spectrophotometric Study on Kinetics of Solvatochromism of Methyl Violet in Aqueous Methanol

The kinetics of the reaction of methyl violet with iodide in aqueous methanol system was studied by spectrophotometric method. The rate of reaction of methyl violet in different alcoholic composition in presence of potassium iodide was observed at pH 4 and 6 at various temperatures (298–318 K). Solvatochromic effect was studied in different percentages of methanol (0–50%). Bathochromic shift was observed with the decrease in polarity of solvent. The color change was attributed to molecule's structure, the delocalization of unit electrical charge causes deepening of color and decrease of delocalization causes fading of color due to reduction of dye. Increase in the rate of reaction was observed with increase in alcoholic content and also affected by potassium iodide salt and increased with increase in concentration of potassium iodide. Energy of activation (E_a) and transition energy (E_T) were calculated with the help of kinetic data. Thermodynamic parameters such as enthalpy change of activation (ΔH*), Gibbs free energy change of activation (ΔG*) and entropy change of activation (ΔS*) were evaluated as a function of concentration of solvent and salt.     

Modified Protein-Water Interactions in CHARMM36m for Thermodynamics and Kinetics of Proteins in Dilute and Crowded Solutions

Proper balance between protein-protein and protein-water interactions is vital for atomistic molecular dynamics (MD) simulations of globular proteins as well as intrinsically disordered proteins (IDPs). The overestimation of protein-protein interactions tends to make IDPs more compact than those in experiments. Likewise, multiple proteins in crowded solutions are aggregated with each other too strongly. To optimize the balance, Lennard-Jones (LJ) interactions between protein and water are often increased about 10% (with a scaling parameter, λ = 1.1) from the existing force fields. Here, we explore the optimal scaling parameter of protein-water LJ interactions for CHARMM36m in conjunction with the modified TIP3P water model, by performing enhanced sampling MD simulations of several peptides in dilute solutions and conventional MD simulations of globular proteins in dilute and crowded solutions. In our simulations, 10% increase of protein-water LJ interaction for the CHARMM36m cannot maintain stability of a small helical peptide, (AAQAA)₃ in a dilute solution and only a small modification of protein-water LJ interaction up to the 3% increase (λ = 1.03) is allowed. The modified protein-water interactions are applicable to other peptides and globular proteins in dilute solutions without changing thermodynamic properties from the original CHARMM36m. However, it has a great impact on the diffusive properties of proteins in crowded solutions, avoiding the formation of too sticky protein-protein interactions.     

高效液相色谱快速测定水产品中孔雀石绿、结晶紫及其无色产物的残留量

采用高效液相色谱同时检测水产品中孔雀石绿、结晶紫及无色孔雀石绿和无色结晶紫的残留量,样品经提取、净化处理后所得残渣用乙腈溶解后,通过采用C_(18)色谱柱,以乙腈(A)和pH3.0的0.02 mol·L~(-1)磷酸二氢钾缓冲溶液(B)按不同比例混合进行梯度淋洗,实现孔雀石绿、结晶紫及其代谢物的分离。用自制的二氧化铅柱氧化无色孔雀石绿及无色结晶紫。在588 nm波长处,测定4种物质的质量浓度在0.3～6.0 mg·L~(-1)范围内与其峰面积呈线性关系,相对标准偏差(n=6)小于2.5%,检出限(3S/N)小于1.9μg·kg~(-1),分析时间20 min。以凤尾鱼罐头为基体进行回收试验,方法的回收率在71.5%～88.6%范围。     

NMR Study on Polymer-Solvent Interactions during Temperature-Induced Phase Separation in Aqueous Polymer Solutions

Some possibilities of NMR spectroscopy (mainly spin-spin relaxation) in investigations of hydration and other polymer-solvent interactions during the temperature-induced phase separation in aqueous polymer solutions are described. A certain portion of water molecules bound in phase-separated mesoglobules was revealed. The residence time of the bound HDO for poly(vinyl methyl ether) (PVME)/D₂O solution (c = 6 wt%) is 1.2 ms. With time a slow release of originally bound water from the respective mesoglobules was observed. For highly concentrated PVME/D₂O solutions (c = 20–60 wt%), the residence time of bound HDO ≫ 2.7 ms and fractions of bound water unchanged even for 70 h were found. A similar behaviour as described above for water (HDO) was also found for EtOH molecules in PVME/D₂O/EtOH solutions.     

微量热法研究α-环糊精与新型表面活性剂的包结作用

在298.15 K下用微量热法研究了α-环糊精与3-烷氧基-2-羟丙基三甲基溴化铵在水溶液中的包结作用.实验结果表明,随着疏水链CnH2n＋1O中碳原子数目n的增加(n=7、8、12、14), 主-客体包合物的化学计量比由1 :1为主变为2 :1为主. 各包合物都相当稳定,对应于n=7、8、12、14所得实验稳定常数分别为,β1=1.95×103 dm3•mol－1、β1=2.62×103 dm3•mol－1、β2=3.06×106 dm6•mol－2、β2=13.75×106 dm6•mol－2.包合物的形成均是焓驱动过程.包合物的平衡常数随烷氧基(CnH2n＋1O)中碳原子数目n的增加而增大,而包合物生成过程的标准反应焓(ΔHΘ)和标准反应熵(ΔSΘ)都随n的增加而减小.从主、客体的微观结构及包合物形成前后表面活性剂离子憎水基团周围溶剂分子排列结构的变化出发对实验结果进行了讨论.